Triazolo triazinones

ABSTRACT

NEW 1,2,3,7 - TETRAHYDRO-(1,2,4)TRIAZOLO(3,2-C)(1,2,4)TRIAZINONE-(7) COMPOUNDS OF THE FORMULA   2-R2,2-R3,3-R4,6-R1,7-(O=)-1,2,3,7-TETRAHYDRO-(1,2,4)-   TRIAZOLO(3,2-C)(1,2,4)TRIAZINE   IN WHICH:   R1 IS HYDROGEN, SUBSTITUTED OR UNSUBSTITUTED ALKYL, ALKENYL, CYCLOALKYL, ARALKYL OR ARYL; R2 AND R3 INDIVIDUALLY ARE HYDROGEN, SUBSTITUTED OR UNSUBSTITUTED ALKYL, ALKENYL, CYCLOALKYL, CYCLOALKENYL OR ARALKYL; AND R2 AND R3 TAKEN TOGETHER, ARE ALKYLENE OF FROM 4 TO 7 RING CARBON ATOMS WHICH MAY CARRY ONE OR MORE ALKYL GROUP SUBSTITUENTS, AND R4 IS HYDROGEN, ALKYL, ALKENYL, ARALKYL OR SUBSTITUTED OR UNSUBSTITUTED SRYL   ARE PREPARED BY A NOVEL SYNTHESIS BY REACTING THE CORRESPONDING DIAMINO DIHYDRO TRIAZINONE COMPOUND WITH AN OXO COMPOUND OF THE FORMULA   R2-CO-R3   IN THE PRESENCE OF A LOWER ALKANOIC ACID. THE NOVEL COMPOUNDS ARE OUTSTANDINGLY EFFECTIVE AS HERBICIDES, E.G., AS SELECTIVE HERBICIDES.

United States Patent Office 3,759,910 Patented Sept. 18, 1973 3,759,910 TRIAZOLO TRIAZINONES Karlfried Dickore and Ludwig Eue, both Farbenfahriken Bayer AG., Leverkusen, Germany No Drawing. Filed Dec. 9, 1970, Ser. No. 96,647 Claims priority, application Germany, Dec. 31, 1969, P 19 65 739.7 Int. Cl. C07d 57/34 US. Cl. 260-2495 21 Claims ABSTRACT OF THE DISCLOSURE New 1,2,3,7 tetrahydro-[1,2,4]triazo1o[3,2-c][1,2,4]- triazinone-(7) compounds of the formula in which:

R is hydrogen, substituted or unsubstituted alkyl, alkenyl,

cycloalkyl, aralkyl or aryl;

R and R individually are hydrogen, substituted or unsubstituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl; and

R and R taken together, are alkylene of from 4 to 7 ring carbon atoms which may carry one or more alkyl group substituents, and

R is hydrogen, alkyl, alkenyl, aralkyl or substituted or unsubstituted aryl.

are prepared by a novel synthesis by reacting the corresponding diamino dihydro triazinone compound with an oxo compound of the formula in the presence of a lower alkanoic acid.

The novel compounds are outstandingly effective as herbicides, e.g., as selective herbicides.

The present invention relates to certain new 1,2,3,7- tetrahydro [1,2,4]triazolo[1,2,41triazinone (7) compounds, and to a novel process for their production. In different aspect, the invention relates to herbicidal compositions containing these compounds and to herbicidal methods.

It is known that 3,7-dihydro-[1,2,4]triazolo[3,2-c] [1,2,4]triazinones-(7), for example 3-benzy1-6-phenyl- 3,7-dihydro-[1,2,4]triazolo[3,2-c][1,2,4]triazinone (7) which has the formula ii t (hm-05m are obtained when 3,4-diaminodihydrotriazinones-(5) are reacted with carboxylic acids or their anhydrides (Chem. Ber. 97, pp. 2173-2178 (1964)). These dihydrotriazolotriazinones possess a slight degree of herbicidal activity. Heretofore, no process for the preparation of 1,2,3,7-tetrahydro-[1,2,4]triazolo[3,2-c] [1,2,4]triazinones (7) has been described in the literature.

It is, furthermore, known that 4-amino-3-thioxo6- methyl-2,3,4,S-tetrahydro-1,2,4-triazinone-(5) reacts with p-nitrobenzaldehyde to give the p-nitrobenzylidene compound (Schiif base) of the formula (see Periodica Polytechnica Hung. 12, pages 259-275 (1968)).

The present invention provides 1,2,3,7-tetrahydro[1,2, 4]triazolo[3,2-c][1,2,4]triazinones-(7) of the formula I H R R2 1 in which:

R is a hydrogen or optionally substituted alkyl (which may be straight-chain or branched), alkenyl, cycloalkyl, aralkyl or aryl radical,

each of R and R independently is hydrogen or optionally substituted alkyl (which may be straight-chain or branched), alkenyl, cycloalkyl, cycloalkenyl or aralkyl radical, or

R and R together are alkylene with 4 to 7 carbon atoms which may carry one or more alkyl group substituents, and

R is hydrogen, alkyl, alkenyl, aralkyl or an optionally substituted aryl radical.

Preferably, R is lower branched. alkyl, and R and R are also preferably lower alkyl or, when taken together, a lower alkylene bridge of, mg. 4 to 6 carbon atoms, in the novel compounds of this invention. R is also preferably lower alkyl.

The present invention also provides a process for the production of a compound of the Formula 1 defined above, in which a 3,4-diamino-4,5-dihydro-1,2,4-triazinone-(5) of the formula in which R, and R have the meanings given above, is reacted with an oxo compound of the formula in which R and R have the meanings given above, in the presence of a lower aliphatic carboxylic acid.

It is decidedly surprising that the reaction described above takes the course stated and leads smoothly to a 1,2,3,7 tetrahydro[1,2,4]triazolo[3,2-c1triazinone-(7) in a high yield. Rather, it would have been expected either that the carbonyl compound of the Formula 3 would react with the 3,4-diamino-4, S-dihydro-1,2,4-triazinone- (5) of the Formula 2 to form a Schiff base of the type (B) (see Periodica Polytechnica Hung. 12, pages 259-275 (1968)) or that the triazinone of the Formula 2 would react with the lower aliphatic carboxylic acid, present as an auxiliary material, with the formation of a 3,7-dihydro- [1,2,4]tr-iazolo[3,2-c] [1,2,4]triazinone-(7) of the type (A) (see Chem. Ber. 97, pages 2l73-2178 (1964) The isomeric Schiff bases can, in general, be obtained by carrying out the condensation of the Compounds 2 and 3 in the presence of strong acids such as mineral acids or organic sulphonic acids.

The process of the invention permits the syntheses, in a simple manner, of numerous new 1,2,3,7-tetrahydro ['1,2,4]triazolo[3,2-c][1,2,4]triazinones, and is therefore a broadly applicable enrichment of the art.

If 4-amino-3-methylamino-6-tert-butyl-4,5 dihydro 1, 2,4-triazinone-(5) and acetone are used as starting materials, the react-ion course can be represented by the following formula scheme mono I N NHZ /CH3 The 3,4-dia-mino-4,5-dihydro-1,2,4-triazinones-() to be used as starting materials are defined generally by the Formula 2. In Formula 2, as in Formula 1, R stands preferably for a branched alkyl radical with 3, 4 or 5 carbon atoms, a cyclohexyl radical or a phenyl group, which may be substituted by chlorine, and R stands preferably for methyl or ethyl.

As examples of the 3,4-diamino-4,5-dihydro-1,2,4-triazinones-(S) which can be used according to the invention, there are mentioned:

3,4-diamino-6- 4-methylcyclohexyl) -4,5-dihydro-1,2,4-

triazinone- (5 3,4-diamino-6-phenyl-4,S-dihydro-1,2,4-triazinone-(5 3 ,4-diamino-6- (3-chlorophenyl) -4,5-dihydro-1,2,4-

triazinone- (5 3 ,4-diamino-6- (4-chlorophenyl) -4,5-dihydro-1,2,4-

triazinone- (5 3 ,4-diamino-6-benzyl-4,5-dihydro 1,2,4-triazinone-(5),

3,4-diamino-6- (2-chlorober'1zyl) -4,5-dihydro- 1 ,2,4-triazinone- 5 3,4-diamino-6- (3-chlorobenzyl -4,5-dihydro 1,2,4-triazinone- 5 3,4-diamino-6-(4-chlorobenzyl)-4,5-dihydro-1,2,4-triazinone- 5) 3,4-diamino-6- (3,4-dichlorobenzyl) -4,5-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6-methyl-4,5-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6-ethyl-4,5-dihydro-1,2,4-triazinone- 5) 4-amino-3 -methy1amino-6-propy1-4,5-dihydrol ,2,4-

triazinone- 5 4-amino-3-methylamino-6-isopropyl-4,S-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6-n-butyl-4,S-dihydro-1,2,4-

triazinone- (5) 4-amino-3-methylarnino-6-isobutyl-4,5-dihydro-1,2,4-

triazinone- (5 4-amino-3-methylamino-6-tert.-butyl-4,5-dihydro-1,2,4-

triazone- 5 4-amino-3-methylamino-6-cyclopentyl-4,5-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6-cyclohexyl-4,S-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6- (4-methylcyclohexyl) -4,5-

dihydro-1,2,4-triazinone- (5) 4-amino-3 -methylamino-6-cycloheptyl-4,5 -dil'1ydro- 1 ,2,4-

triazinone- 5 4-amino-3-methylamino-6-pheny1-4,5-dihydro- 1 ,2,4-

triazinone- (5 4-amino-3-methylamino-6- 4-methylphenyl) -4,5-dihydro- 1,2,4-triazinone-( 5 4-amino-3-methylamino-6- (4-isopropylphenyl -4,5-di

hydro-1,2,4-triazinone-(5) 4-amino-3 -methylamino-6- (4-tert.-butylphenyl) -4,5-dihydro-1,2,4-triazinone-(5),

4-amino-3-methylamino-6- (2-chlorophenyl) -4,5-dihydro- 1,2,4-triazinone- 5 4-amino-3-methylamino-6- 3-chlorophenyl )-4,5-dihydro- 1,2,4-triazinone- (5 4-amino-3-methylamino-6- (4-chloropheny1) -4,5-dihydro- 1,2,4-triazinone- 5 4-amino-3 -methylamino-6- 3,4-dichlorophenyl) -4,5-dihydro-1,2,4-triazinone-(5 4-amino-3 -methylamino-6-benzyl-4,5-dihydro-1,2,4-

triazinone (5 4-amino-3-methylamino-6-cyclohexylmethyl-4,S-dihydro- 1,2,4-triazinone- 5 4-amino-3-methylamino-6- (2-chlorobenzyl -4,5-dihydro- 1,2,4-triazinone- (5 4-amino-3-methylamino-6- (3-chlorobenzyl -4,5-dihydr0- 1,2,4-triazinone- 5 4-amino-3-methy1amino-6-(4-chlorobenzyl)-4,5-dihydro- 1,2,4-triazinone- 5 4-amino-3-methylamino-6-( 3,4-dichlorobenzyl -4,5-dihydro-1,2,4-triazinone-(5),

4-amino-3 -methylamino-6-propenyl-4,5 dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6-cinnamyl-4,S-dihydro-1,2,4-

triazinone- 5 4-amino-3-methylamino-6- a-phenylethyl) -4,5-dihydro- 1,2,4-triazinone- 5 I 4-amino-3-methylamino-6- (,B-phenylethyl -4,5-dihydro- 1,2,4-triazinone-(5),

4-amino-3-methylamino-6- (Z-methylbutyl) -4,5-dihydro- 1,2,4,-triazinone-(5 4-amino-3 -methylamino-6- 2-methylpropyl) -4,5 -d1hydrm 1,2,4-triazinone- 5 4-amino-3-methylamino-6-isopropenyl-4,5-dihydro-1,2,4-

triazinone-(S 4-amino-3 -methylamino-6-cyclohexen-( l -yl-4,5-d1hydro- 1,2,4-triazinone- (5 4-amino-3 -ethylamino-6-isopropyl- 4, 5-dihydro-1,2,4-

triazinone-(S),

4- amino-3 -ethylamino-6-methyl- 4, 5 -dihydro- 1,2,4-t11- azinone- 5 4-amino-3-ethylamino-6-propy1-4,5-dihydro-1,2,4-

triazinone-(S 4-amino-3-ethylamino-6-n-butyl-4,S-dihydro-1,2,4-

triazinone- (5 4-amino-3-ethylamino-6-isobutyl-4,5-dihydro-1,2,4-

triazinone-( 5 4-amino-3 -ethylamino-6-tert.-butyl-4,S-dihydro-1,2,4

triazinone-( 5 4-amino-3-ethylamino-6-cyclohexyl-4,5-dihydro-1,2,4-

triazinone-( 5) 4-amino-3 -ethylamino-6-cyclohexylmethyl-4,5 -dihydro- 1,2,4triazinone- 5 4-arnino-3-ethylamino-6- (4-methylcyclohexyl) -4,5-

dihydro-1,2,4-triazinone-(5),

4-amino-3-ethylamino-6-benzyl-4,S-dihydro-1,2,4-triazinone-(S),

4-amino-3 -ethylamino-6-phenyl-4,5-dihydro-1,2,4-tr1azinone- 5 4-amino-3 -ethylamino-6- (3 ,4-dichlorophenyl) -4, 5-

dihydro-1,2,4-triazinone-(5 4-amino-3 -n-butylamino-6-isopropyl-4,5-dihydro-1,2,4-

triazinone- 5 4-amino-3-dodecylamino-6-isopropyl-4, S-dihydro- 1 ,2,4-

triazinone- (5 4-amino-3-anilino-6-isopropyl-4,5-dihydro-1,2,4-triazinone- 5) 4-amino-3-n-butylamino-6-cyclohexyl-4,5-dihydro-1,2,4-

triazinone- (5 4-amino-3 -n-butyl amino-6-tert.-butyl- 4,5 -dihydro-1 ,2,4-

triazinone- (5 4amino-3-benzylamino-6-isopropyl-4,5-dihydro-l,2,4-

triazinone- (5 4-amino-3-benzylamino-6-tert.-butyl-4,5-dihydro-1,2,4-

triazinone- 5 4-amino-3-benzylamino-6-cyclohexyl-4,S-dihydrol ,2,4-

triazinone- 5 4-amino-3-benzylamino-6-phenyl-4,5-dihydro-1,2,4-

triazinone-( 5 4-amino-3 -allylamino-6-isopropyl-4,S-dihydrol ,2,4-

triazinone-( 5 4-amino-3-allylamino6-tert.-butyl-4,5-dihydro-1,2,4-

triazinone- (5 4-amino-3-allylamino-G-cyclohexyl-4,S-dihydro- 1,2,4-

triazinone- (5 4-amino-3-allylamino-6-phenyl-4,5-dihydro-1,2,4-triazinone- 5 4-amino-3-methylamino-4, S-dihydro-1,2,4-triazinone-(5 4-amino-3-ethylamino-4,5-dihydro-1,2,4-triazinone-(5 4-amino-3-benzylamino-4,S-dihydro-1,2,4-triazinone-(5 Some of the 3,4-diamino-4,5-dihydro-1,2,4-triazinones- (5) of the Formula 2 used as starting materials are known (see Chem. Ber 97, pages 2173-2178 and Belgian Patent Sepecification 697,083). The not-yet-known triazinones can be prepared according to known methods by cyclisation of u-oxocarboxylic acids with diaminoguanidines or by aminolysis of 4-amino-3-alkylmercapto-4,5- dihydro 1,2,4 triazinones (5) (see the preparative examples herein).

The oxo compounds of the Formula 3 used as starting materials are all known. As examples of aldehydes and ketones which can be used, there are mentioned: formaldehydc, acetaldehyde, propionaldchyde, n-butyraldehyde,

isobutyraldehyde, valeraldehyde, isovaleraldehyde, tetrahydrobenzaldehyde, hexahydrobenzaldehyde, cinnamaldehyde, hydrocinnamaldehyde, chloral hydrate, pivalaldehyde, acetone, methyl-ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, methylisopropyl ketone, trichloroacetone, trifluoroacetone or hexafluoroacetone.

As diluents for the reaction of the preparative process, all inert organic solvents are suitable. The preferred solvents include hydrocarbons, such as benzine, benzene and toluene; ethers, such as dioxane and tetrahydrofuran; and chlorinated hydrocarbons, such as chlorobenzene or the dichlorobenzenes.

It is, however, expedient to carry out the reaction without the use of a solvent and, instead, to use an excess of the lower aliphatic carboxylic acid necessary as an auxiliary material. Carboxylic acids with from 1 to 5 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid, can be used for this purpose; acetic acid is the preferred carboxylic acid.

The reaction temperature can be varied within a fairly wide range. In general, the work is carried out at from 20 to 120 0., preferably from 50 to C.

The use of pressure is, in general, not necessary. Oxo compounds gaseous at room temperature however, can be reacted in an autoclave.

When carrying out the process according to the invention, 1 to 20 moles of the 0x0 compound of the Formula 3 and 0.1 to 20 moles of the lower aliphatic carboxylic acid are generally used to 1 mole of the 3,4-diamino-4,5- dihydro-1,2,4-triazinone-(5) of the Formula 2 and the mixture is heated until the end of the reaction. Preferably, the oxo compound and the carboxylic acid are used in excess.

The isolation of the reaction products can be effected by evaporation of the reaction mixture or, where watermiscible oxo compounds and carboxylic acids are used, by pouring into water and subsequently effecting suction filtration of the precipitated reaction product. If necessary, the reaction products can be purified in any customary manner, for example by recrystallisation from organic solvents.

The new 1,2,3,7 tetrahydro [1,2,4]triazolo[3,2-c] [1,2,4]triazinones-(5) according to the invention have herbicidal properties and can therefore be used for the control of weeds.

By weeds in the widest sense are meant all plants which grow in places where they are not wanted. Whether the active compounds according to the invention act as total or selective herbicidal agents depends on the amount of active compound applied.

The substances according to the invention can be used for example in the case of the following plants: dicotyledons, such as mustard (Sinapis), cress (Lepidium), cleaver (Galium), common chickweed (Stellaria), mayweed (Matricaria), smallflower Galinsoga (Galinsoga), fathen (Chenopodium), stinging nettles (lUrtica), groundsel (Senecio), cotton (Gossypium), beets (Beta), carrots (Daucus), beans (Phaseolns), potatoes (Solanum), coffee (Coflea); monocotyledons, such as timothy (Phleum), bluegrass (Poa), fescue (Festuca), goosegrass (Eleusine), foxtail (Setaria), ryegrass (Lolium), cheat (Bromus), barnyardgrass (Echinochloa), maize (Zea), rice (Oryza) oats (Avena), barley (Hordeum),

wheat (Triticum), millet (Panicum), sugar cane (Saccharum).

The new compounds show an excellent selectivity in respect of cereals. They can therefore be used for selective weed control in cereals, for example maize, sorghum, oats, wheat, barley and rice; application should take place chiefly between sowing and emergence of the cultivated plants. In addition, some compounds are also suitable for selective weed control after the emergence of the cultivated plants, that is to say according to the postemergence process. In the case of application before emergence of the cultivated plants, the weeds can also be combated selectively in other cultivations, for ex ample in cotton, potatoes, peas, soya, beans and flax.

The active compounds according to the present invention can be converted into the usual formulations, such The active compounds'may be used as such or in the form of their formulations or of the applications forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates. Ap-

as solutions, emulsions, suspensions, powders, pastes and plication may be eifected in the usual manner, for exgranulates. These may be produced in known manner, ample by dusting, spraying, squirting, watering and for example by mixing the active compounds with exscattering. tenders, that is, liquid or solid diluents or carriers, op- The amount of active compound applied may vary tionally with the use of surface-active agents, that is, within fairly wide ranges. It depends essentially on the emulsifying agents and/or dispersing agents. In the case nature of the desired efiect. In general, the amounts apof the use of water as an extender, organic solvents can, plied are from 0.1 to 20 kg., preferablyfrom l to 10 kg. for example, also be used as auxiliary solvents. of active compound per hectare.

As liquid diluents or carriers, there are preferably The present invention also provides a herbicidal comused aromatic hydrocarbons, such as xylenes or benzene, position containing as active ingredient a compound of chlorinated aromatic hydrocarbons, such as chlorobenthe present invention in admixture with a solid diluentor zenes, parafiins, such as mineral oil fractions, alcohols, carrier or in admixture with a liquid diluent or carrier such as methanol or butanol, or strongly polar solvents, containing a surface-active agent. such as dimethyl formamide or dimethyl sulphoxide, as The present invention also provides a method of com well as water. bating weeds which comprises applying to the Weeds or a As solid diluents or carriers, there are preferably used weed habitat a compound of the present invention alone ground natural minerals, such as kaolins, clays, talc or or in the form of a composition containing as active inchalk, or ground synthetic minerals, such as highlygredient a compound of the present invention in admixdispersed silicic acid or silicates. ture with a solid or liquid diluent or carrier.

Preferred examples of emulsifying agents include nonr The present invention further provides crops protected ionic and anionic emulsifiers, such as polyoxyethylenefrom damage by Weeds by being grown in areas in which fatty acid esters, polyoxyethylene-fatty alcohols ethers, immediately prior to and/or during the time of the growfor example alkylarylpolyglycol ethers, alkyl sulphonates ing a compound of the present invention was applied and aryl sulphonates; and preferred examples of dispersalone or in admixture with a solid or liquid diluent or ing agents include lignin, sulphite waste liquors and carrier. It will be seen that the usual methods of providing methyl cellulose. a harvested crop may be enhanced by the present inven- The active compounds according to the invention may tion. be present in the formulations in admixture with other The activity of the compounds of the present invention active compounds. The formulations contain, in general, is illustrated in and by the following examples, in which from 0.1 to 95, preferably from 0.5 to 90, percent by the following test compounds, illustrative of the novel weight of active compound. compounds, were used.

TABLE 1 Compound No. Chemical name Structure 1 2,2,3-trimethy1-6-tert.-butyl-1,2,3,7-tetrahydro-[1,2,4]-trlazolo[3,2-c][1,2, fl-trlazinone-(7) NH mono-K CH3 \N/ /\CHZ CH;

2 2-etl)ryl-2,3-dimethyl-6-tert.-butyl-1,2,3,7-tetrahydro-[1,2,4]-trlazolo[3,2-c][1,2,41-triazinone- (d (HzC):C-l CHa x i 0 H N 2 I 3 2-1sopropyl-3-methyl-6-tert.-butyl-1,2,3,7-tetrahydro-[1,2,4]-trlazolo-l3,2-c][1,2,4l-trlazl- (Ill none-(7 N/NH (HaChC- H I J N Y \N/ s)2 III CH1 4 2,2pentamethylene-3-methy]-6-tert.-bntyl-1,2,3,7-tetrahydro-[l,2,4]-trlazolo-[3,2-e][1,2,4]-

trlazlnone-(7).

mmzqfili g TABLE 1-0ontinued Compound No. Chemical name Structure 5 2,3-dimethyl-2-lsopropyl-6-tert.-buty1-1,2,3,7,-tetrahydro-[1,2,41-tr1azolo-[3-2'c][1,2,4]- O trizainone-(7).

N (11:0):10 I OH N j Omen),

6. 2, 2, 3-trlmethyl-6-phenyl-1, 2, 3, T-tetrahydro-fl, 2, 4]-triazolo-[3, 2-e]-[l, 2, 41-triazinone-(7)..

NH I CH; N

\N/ CH3 N (BH:

7 2,2,B-trimethyl-fi-isopropyl-l,2,3,7-tetrahydro-[l,2,4]-triazo1o-l3,201-[1,2,4]-trlazinone-(7) ,NH (HI 2 C HKN C H N d'\ CH: H:

8 2,2-pentamethylene-3-methyl-6-isopropyl-1,2,3,7-tetrahydro-[1,2,4)-triazolo-[3,2-c]-[1,2,4]- O triazinone-(7).

EXAMPLE A Pro-emergence test Solvent: parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the test plants was determined and characterized by the values 0-5, which have the following meaning:

0 no effect 1 slight damage or delay in growth 2 marked damage or inhibition of growth 3 heavy damage and only deficient development or only 50% emerged 4 plants partially destroyed after germination or only 25% emerged 5 plants completely dead or not emerged The active compounds, the amounts applied and the results obtained can be seen from the following table:

TABLE A Pro-emergence test Active compound applied, kg./ Eehi- Cheno- Stel- Galln- Matri- Active compound hectare nochloa podium Slnapls laria Lolium soga caria Oats Cotton Wheat Maize (Compound A):

0 0 0 I N N Hr-(LH; I (known) Compound 1 10 5 6 5 l5 5 a a 4 a a s B 5 6 5 5 6 5 5 3 5 1 5 2.5 6 5 6 6 4'45 5 B 1 4 0 445 1. 25 5 5 4 l5 4 5 6 0 4 0 4 Compound 2 10 6 5 B 6 5 5 5 5 5 6 5 B 5 5 5 i5 5 6 5 5 5 i5 6 2.6 5 5 6 5 4-5 6 5 5 5 4 4 1.25 5 5 i 5 4 5 5 4 5 2 3 TABLE A-Continued compound i L v V applled,'kg.l Echi- Cheno- Stel- Galin- Matrl- Active compound hectare noehloa podium" Sinapis 'laria Lfolium soga' 'carla Oats Cotton Wheat Maize Oompound3 1o 5 5 n a 1s 1s 5 i a 4 2 a 5 5 5 5 5 4 5 5 2 3 l 1 2.5 5 5 4-5 5 3 5 5 1 2 0 1.25 4-5 4 3 4-5 2 5 0 0 0 0 C0mp0und.4l 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 4 4-5 4 2.5 5 5 5 4-5 3-4 5 5 4 4 4 3-4 v 1. 5 5 5 4 2 5 5 3 4 2-3 3 Compound 5 10 5 5 5 5 5 5 5 5 3 2-3 3 5 5 5 5 5 4-5 5 5 4' 1-2 1 2 2.5 5 5 4 5 4 5 5 3 0 0 0 1.25 4-5 4-5 3 5 3 5 5 2 0 0 0 Compoundfi 10 5 5 5 5 5 5 5 5 3 3 4 5 5 5 5 5 5 5 5 4-5 2 2 3 2.5 5 5 4-5 5 5 5 5 4 1 0 1 1.25 5 5 4 5 4-5 5 5 3 0 0 0 Compound? 10 5 5 5 5 5 5 5 5 5 4 3 5 5 5 5 5 5 5 5 4-5 5 4 2 2.5 5 5 5 5 4-5 5 5 3 4 3 1 1. 25 4-5 4-5 5 5 4 5 5 2 3 .2. 0

Compound 8 10 5 5 5 5 5 5 5 3 4 3-4 3 5 5 5 5 5 5 5 5 2 4 3 2 2.5 4-5 4-5 5 5 4-5 5 5 1 4 2 0 1. 25 4-5 4 5 5 4 5 5 0 2-3 0 0 EXAMPLE B on the concentration of the spray liquor, the amount of Post-emergence test Solvent: 5 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether 0 no effect water applied lies betwen 1000 and 2000 liters/hectare. After three weeks, the degree of damage to the plants was determined and characterized by the values 0-5, which have the following meaning:

1 a few slightly burned spots 2 marked damage to leaves' 3 some leaves and parts of stalks-partially dead 4 plant partially destroyed 5 plant completely dead The active compounds, their concentration and the which were stated in the table were applied. Depending 40 results obtained can be seen from the following table:

TABLE B Post-emergence test Active compound ap led, Echi- Cheno- Galin- Stel- Matri- Activecompound kgJhectare noohloa podium Sinapis soga laria Urtica caria Daucus Oats Cotton Wheat (C p u .r a .l o v F e.

0 8 3 0 4-5 3 3 3 2 2 1-2 1-2 0 N a 2 a t a a i l 1 0 I 1 0 V WW ,1 -7 U I 0 0 Compound 1 2 5 5 5 5 5 5 5 5 5 5 5 1 4-5 5 5 5 5 5 5 5 4-5 5 4 0.5 4-5 5 5 5 5 5 5 5 4 5 4 0.25 4 5 5 5 5 5 5 5 3 5 3 cam oahaaa; 2' 5 5 5 5' 5 "5"" is" '5 '5' v15 1 5 5 5 5 5 5 5 5 4 5 4 0.5 5 5 5 5 5 5 5 5 3-4 5 3-4 0.25 4 5 5 5 5 5 4-5 4 3 5 8 'comisound's...'.-..'; -'.'L. '2 5 Y Y 5 5 5" 5 5 5 5 3 "5" 2 1 4-5 5 5 5 5 5 5 5 1-2 3 1 0 5 4-5 5 5 5 5 5 5 5 1 2-3 0 4 5 5 5 4-5 4' 4 4-5 0 2 0 14 The following examples illustrate the process of the Into a boiling solution of 2360 grams 4-amino-3-methinvention. yl-mercapto-6-tert.-butyl 4,5 dihydro 1,2,4-triazinone- EXAMPLE 1 (see Japanese patent specification 547,317) in 770 Preparation of 2 2 3 trimethyl 6 tertrbutym 2 3 ml. glacial acetic acid and 4000 ml. isopropanol there was introduced, after the addition of 28 grams p-toluene sultetrahydm [124]tnazole[32 c][124]maZmne (7) 5 fonic acid, monomethylamine for 56 hours. After cool- 0 ing, the crystallized reaction product was filtered off with NH suction. A further portion was obtained from the filtrate (make I N CH1 after stirring the latter together with water.

N Yield: 1978 grams (91% of the theory); M.P. 234 C. N In an analogous manner, the following new 1,2,3,7- tetrahydr0-[1,2,4]tr1azolo[3,2-c] [1,2,41-triazinones (7) of the Formula 1 can be prepared:

TABLE 2 Reaction product (1) Starting materials EX. M.P. No. Triazinone (2) 01:0 compound (3) R1 R: R: R (3,)

2 4-amino-3-methylamino-6-tert.-butyl-4,5-dihydro-1,2,4- Gyclohexanone t-C4Hn -(CzH )5- OH; 146

triazinone-(5), M.P. 234 C. 3 rln Cyclopentanone t-CqHc --(CH2)4- CH; 132 4 (in Methyl-isopropyl ketone. t-C4Ho CH3 i-C3H OH; I 142 5 rln Methyl ethyl-ketone t-CrHq CH3 C2Hs OH, I 131 6 do Isovaleraldehyde t-C4Hn H i-GqHn CH; 116

7 do Hexahydrobenzaldehyde.. t-CiHn H H OH; 144

3 rin Isobutyraldehyde t-CtHfl H i-C3H1 OH; 153 9 4-amino-3-ethylamino-6-tert.-butyl4,5-dihydro-1,2,4- Cyclohexanone t-GiHn -(CH2) 0 H; 18o

triazinone-(fi), M.P. 178 0. 1o 4-amin0-3-methylarnino-6-isopropyl-4,5-dihydr01,2,4- Acetone i-CaH1 OH; OH; CH 1 5 triazinone-(fi), M.P. 142 C. 11- do Cyclohexanone i-CzH? -(CH2) CH; 173 12. do hloral- 1-03111 H con CH :1 13- mino-3-ethylamino'fi-isopropyl-i,5-dihydro-1,2,4- Acetone. i-CaH1 CH; CH; 0 H; 110

triazinone-(5), M.P. 158 C. 14.... 4-amino-3-n-bntylamino-6-lsopropyl-4,5-dihydro-1,2,4- .....do i-C H CH; CH; n-O4Hn 187 triazinone-(B), M.P. 125 0. UL... 4-amino'3-n-dodecylamino-ti isopropyl-j-dihyd.ro- Cyclohexanone... i-CaH-i (C2H)5- n-CizH 1,2,4-triazinone-(5), M.P. 104 C. 16. 4-amino-3-anilino e-isopropyl-j-dihydro-l,2,4-triazi- Acetone i-C3H1 CH| CH; CQH5 167 none-(5), M.P. 162 C. do... Cyclohexanonm..... l-C3H7 -(CH2) 0 H; 169 18 4-amino-3-benzylamino6-is0propyl-4,54iihydro-1,2,4- -....d0 i-CaH7 (CHz)s- GHQ-05H 150 tr'lazinone-(fi), M.P. 144 C.

19 4-amino-3-methylamino-6-eyclehexyl-4,B-dihydro-1,2,4- Acetone CH; CH; CH; 91

triazinone-(fi), M.P. 141 C. H

20 rin Cyclohexanone Same (CH2)5 CH; 85 21"-.. 4-ami110-3-n-butylamtno-6cyclohexyl-4,5-dihydro-1,2,4- do ..do -(CH2) Il-C4Hg 176 triazinone-(6), M.P. 173 C. 22. banino-3-methylamino-6-methyl-4,5-dihydro 1,2,4-tria- Acetone CH3 CH1 CH CH 131 zinone(5), M.P. 180 C. 23 .do Cyclohexanone CH3 -(CH2) CH3 168 24.-. 4-amino-3-methylarnino-6-phenyl-4,5-dihydro-1,2,4-tria- Acetone CuH5 CH CH CH; 179

zinone-(fi), M.P. 212 C. 25 do Cyclohexanone 00H; (OH2)i-- CH; 204

l Decomposition.

The starting material for Example 9, 4amine-3-ethylamino-6-tert.-butyl-4,5-dihydro-1,2,4-triazinone-(5), can be prepared as follows: 350 grams 4-arnino-itmethylmercapto-6-tert.-butyl-4,5-dihydro-1,ZA-triazinoneifi) were suspended in a mixture of 820 ml. isopropanol and 114 ml. glacial acetic acid. At reflux temperature, gaseous ethylamine was introduced into the reaction mixture. Boiling under reflux was then efiected for a further 5 hours, followed (after cooling) by curing into 4 liters of cold water, while stirring, and then efiecting suction filtration oi the precipitated reaction product. Crude yield: 251 grams (7247 of the theory). After recrystallization from 1 liter of toluene, 224 grams (65%pure product) of M.P. 178 C. were obtained.

From 126 (decomposition).

4 N 01: sharp from 50.

A mixture of 19.7 grams 4-amino-3-methylamino-6- What is claimed is:

tert.-butyl-4,5-dihydro-1,2,4-triazinone-(5), 50 ml. acetone 1. 1,2,3,7 tetrahydro-[1,2,4]triazolo[3,2-c] [1,2,4]-triand 50 ml. acetic acid was heated for one hour on a boilazinone-(7) compound of the formula ing water bath. Concentration was then effected and the crystalline residue remaining after thorough heating in a 0 vacuum was recrystallized from 150 ml. benzene. There H g were obtained 21.6 grams (91% of the theory) of pure R1-]{ 1 R, 2,2,3-trimethyl-6-tert.-butyl 1,2,3,7 tetrahydro-[l,2,4] l 2 triazoio[3.2-c] [1,2,4]triazin0ne-(7) of MP. 165-168 E4, 3 a, C. (decomp.). N f

The same compound was obtained when the acetic acid 7 R4 was replaced by formic aciid, propionic acid, butyric acid i hi h; of lsoblltyfiq acld- R is hydrogen, lower alkyl of up to 5 carbon atoms, The Y Y Y -L A- alkenyl of up to 3 carbon atoms, cycloalkyl of from triazinone-(S) required as the starting material can be 5 to 7 ring carbon atoms, benzyl, phenethyl or prepared as follows: phenyl wherein said alkyl, alkenyl, cycloalkyl, ben

zyl, phenethyl, or phenyl may be substituted with at least one halogen or lower alkyl;

R and R individually are hydrogen, alkyl of from 1 to carbon atoms, cycloalkyl or about 6 ring carbon atoms, or benzyl; and

R and R taken together, are alkylene of from 4 to 7 ring carbon atoms which may carry one or more alkyl group substituents; and

R is hydrogen, alkyl of from 1 to 4 carbon atoms,

alkenyl of up to 3 carbon atoms, benzyl, or phenyl.

2. Compound as claimed in claim 1 wherein R is branched alkyl of from 3 to 5 carbon atoms.

3. Compound as claimed in claim 1 wherein R is cyclohexyl.

4. Compound as claimed in claim 1 wherein R is phenyl or chlorophenyl.

5. Compound as claimed in claim 1 wherein R is alkyl of from 1 to 4 carbon atoms.

6. Compound as claimed in claim 1 wherein R and R are individually hydrogen or lower alkyl of up to about 5 carbon atoms.

7. Compound as claimed in claim 1 wherein said compound is designated as 2,2,3-trimethyl-6-tert.-butyl-1,2,3,7- tetrahydro-[1,2,4]-triazolo[3,2-c] [1,2,4] -triazinone-(7) 8. Compound as claimed in claim 1 wherein said compound is designated as 2-ethyl-2,3-dimethyl-6-tert.-butyll,2,3,7-tetrahydro [1,2,4] triazo1o[3,2-c] [1,2,4]-triazinone-(7).

9. Compound as claimed in claim 1 wherein said com pound is designated as 2-isopropyl-3-methyl-6-tert.-butyl- 1,2,3,7-tetrahydro [1,2,4] triazolo[3,2-c] [1,2,4]-triazinone-(7).

10. Compound as claimed in claim 1 wherein said compound is designated as 2,2-pentamcthylene-3-methyl-6- tert. butyl 1,2,3,7 tetrahydro-[1,2,4]-triazolo[3,2-c] [1,2,4]-triazinone-(7 11. Compound as claimed in claim 1 wherein said compound is designated as 2,3-dimethyl-2-isopropyl-6- tert. butyl 1,2,3,7 tetrahydro-[1,2,4]-triazolo[3,2-c] [1,2,4]-triazinone-(7 12. Compound as claimed in claim 1 wherein said compound is designated as 2,2,3-trimethyl-6-phenyl-1,23,7- tetrahydro-[1,2,4]-triazolo-[3,2-c] [1,2,4] -triazinone-(7 13. Compound as claimed in claim 1 wherein said compound is designated as 2,2,3-trimethyl-6-isopropyl-1,2,3,7- tetrahydro-[1,2,4]-triazolo[3,2-c] [1,2,4] -triazinone- (7).

14. Compound as claimed in claim 1 wherein said compound is designated as 2,2-pentamethylene-3-methyl-6-iso- N C I in which R and R have the meanings given in claim 1, with an oxo compound of the formula R2 O=C/ in which R and R have the meanings giveninlclaiml, in the presence of a lower alkanoic acid.

16. A process as claimed in claim 15 in which the reaction is carried out at 20 to 120 C. a i

17. A process as claimed in claim 15 in which the reaction is carried out at to C.

18. A process as claimed in claim 15 in which the reaction is carried out in the presence of an inert organic solvent.

19. A process as claimed in claim 15 in which the lower aliphatic carboxylic acid is acetic acid.

20. Process as claimed in claim 15 wherein R and R are lower alkyl and wherein R and R are individually hydrogen or lower alkyl and, together, lower alkylene of from 4 to 7 carbon atoms.

21. Process as claimed in claim 15 wherein R is cycloheXyl, phenyl or chlorophenyl, R is lowerv alkyl and R and R are individually hydrogen or lower alkyl and, together, lower alkylene of from 4 to 7 carbon atoms.

References Cited UNITED STATES PATENTS 3,331,840 7/1967 Fry et a1 260249.5 3,398,148 8/1968 Fry et al 260249.5 3,549,631 12/1970 Lewis et al 260249.5

JOHN M. FORD, Primary Examiner U.S. c1. X.R. 71-93 

